Nitrogen isotope systematics and origins of mixed-habit diamonds
Introduction
Nitrogen is an important component of all of Earth’s major reservoirs, being present in the biosphere, atmosphere, crust and mantle and predicted in the core, but there are very large differences between these reservoirs in terms of their nitrogen concentrations and isotopic compositions (Busigny and Bedout, 2013). It is these differences and how nitrogen cycles between the reservoirs that gives nitrogen the potential to be an important geochemical tracer (e.g. Halama et al., 2010). However, before nitrogen isotope data can be used effectively, its behavior in the various environments needs to be better understood. Much of our understanding of nitrogen in the mantle comes from the investigation of cratonic diamonds. As nitrogen is the most common impurity in diamond, it can compliment carbon isotope data in tracing the deep carbon cycle through time (Javoy et al., 1984, Boyd et al., 1987, Boyd et al., 1992, Boyd and Pillinger, 1994, Cartigny et al., 1997, Cartigny et al., 1998a, Cartigny et al., 1998b, Cartigny et al., 2001, Cartigny et al., 2003, Cartigny et al., 2004, Cartigny et al., 2009, Harte et al., 1999, Bulanova et al., 2002, Bulanova et al., 2014, Hauri et al., 2002, Gautheron et al., 2005, Klein-BenDavid et al., 2010, Smit et al., 2014, Thomassot et al., 2007, Thomassot et al., 2009, Palot et al., 2009, Palot et al., 2012, Mikhail et al., 2013, Mikhail et al., 2014).
Nitrogen concentrations in diamonds range from 0 to ∼>5000 ppm, and in general nitrogen is strongly enriched in diamonds relative to primitive mantle concentrations (Stachel and Harris, 2009). The mean nitrogen isotope value (δ15N) for peridotitic diamonds is −5 ± 4‰ (Cartigny et al., 2014), however, the range reported for all cratonic diamonds is very large (∼−40‰ to ∼+20‰; Cartigny and Marty, 2013), and the variations seen in individual samples can also be as much as 30‰ (Mikhail et al., 2014). Before assuming these data reflect δ15N heterogeneity in the mantle, constraints on the behavior of nitrogen during diamond formation (e.g. compatibility, isotopic fractionation between growth sectors within the diamond, isotopic fractionation between the diamond and fluid/melt growth medium) need to be better understood. To provide further insights into some of these problems, this study will determine the nitrogen isotope systematics of mixed-habit diamonds.
Mixed-habit diamonds are examples of crystals that form by two growth mechanisms occurring at the same time (Frank, 1967); namely octahedral and cuboid growth (Moore and Lang, 1972, Lang, 1974, Suzuki and Lang, 1976a, Suzuki and Lang, 1976b). Octahedral growth produces the flat {1 1 1} faces that define the iconic diamond-crystal morphology, while cuboid growth produces hummocky, non-faceted surfaces whose mean orientation is {1 0 0}, but can be inclined by up to 30°. Crystal-growth theory of diamond (see review by Sunagawa (2005)) shows that the {1 1 1} faces are smooth interfaces on which layer or spiral growth is expected to occur, while the {1 0 0} faces are rough interfaces on which growth occurs by an adhesive-type mechanism. Although rough faces would be expected to grow much more rapidly than smooth ones and therefore grow themselves out of the crystal (Moore, 1985), it is thought that solute–solvent interaction and/or impurity absorption can reduce the growth rate of the rough crystal faces (Palyanov et al., 2010). This prevents them from growing out of the crystal, and allows them to remain as large as the smooth octahedral, habit-controlling faces (Sunagawa, 2005).
Having two different growth mechanisms occurring within a single crystal produces different impurity characteristics between the two growth sectors. Nitrogen concentrations in mixed habit diamonds are often very high (900 to >2000 ppm) and N is preferentially partitioned into the octahedral sectors; with enrichment ranging from 107% to 157% relative to the cuboid sectors (Welbourn et al., 1989, Lang et al., 2004, Rondeau et al., 2004, Zedgenizov and Harte, 2004, Howell et al., 2012, Howell et al., 2013a). While nitrogen-aggregation levels can vary from 0% to 100% IaB, there seems to be no unanimity in the literature regarding differences between the sectors. However, two recent studies (Howell et al., 2012, Howell et al., 2013a) have shown compelling evidence that the rate of nitrogen aggregation does not differ between sectors, but that the subsequent rate of platelet formation can be retarded in cuboid sectors due to the presence of “disc-crack-like” defects (Walmsley et al., 1987). Hydrogen-related absorption features are significantly stronger in the cuboid sectors (Rondeau et al., 2004, Howell et al., 2012, Howell et al., 2013a), most likely due to C–H bonding occurring on the internal surfaces of the disc-crack-like defects. However, due to the possible abundance of IR-inactive hydrogen within a diamond (Sellschop, 1992, Sweeney et al., 1999), there remains no quantitative evidence regarding hydrogen partitioning between growth sectors. Spectroscopic studies have revealed evidence of nickel-related defects in the cuboid sectors (Welbourn et al., 1989, Lang et al., 2007, Howell et al., 2013a). Subsequent laser-ablation inductively-coupled-plasma mass spectrometry (LA-ICPMS) analysis of mixed-habit diamonds (Howell et al., 2013b) confirmed the preferential partitioning of Ni, as well as Co, into the cuboid sectors. Ni concentrations ranged from 3.6 to 36 ppm, and Co from 0.1 to 1.3 ppm, with enrichment relative to the octahedral sectors ranging from 10 to 460 times and 10 to 100 times, respectively. Carbon-isotope analysis via both gas-sourced mass spectrometry (Cartigny et al., 2003) and secondary-ion mass spectrometry (SIMS; Bulanova et al., 2002, Zedgenizov and Harte, 2004, Howell et al., 2012, Howell et al., 2013a) has revealed no evidence of isotopic fractionation between the growth sectors.
The same partitioning of nitrogen into {1 1 1} sectors is seen in high-pressure high-temperature (HPHT) synthetic cubo-octahedral diamonds, but this is accompanied by significant kinetic nitrogen isotopic fractionation (∼30‰; Boyd et al., 1988). To date, two studies have investigated this nitrogen isotopic fractionation in natural mixed-habit diamonds. The first study used SIMS on a mixed-habit diamond from the Mir kimberlite (Yakutia, Russia; Bulanova et al., 2002). While no fractionation between the two growth sectors was reported, this was not the primary focus of the study. The diamond had δ15N values of ∼−3‰ for the bulk of the crystal (core and intermediate zones) with a few values of +8.6‰ to +9.3‰ in the rim zone. However, it should be noted that δ15N analyses via SIMS at that time had an analytical precision of ±2‰, and accuracy of ±8‰ (2σ; Hauri et al., 2002). This means that any isotopic fractionation <2‰ could not have been detected.
The second study of nitrogen isotopes in a mixed-habit diamond was by Cartigny et al. (2003), which used gas-sourced mass spectrometry following the combustion of the sample. While that study also found no nitrogen-isotope fractionation (a 0.1‰ difference between growth sectors with 0.5‰ analytical uncertainties), our interpretation of the cathodoluminescence (CL) image of the sample used (Fig. 1 in Cartigny et al. (2003)), is that this sample was not actually of mixed habit. The CL reveals smooth flat growth in the “cubic” sector, as opposed to the hummocky/curved layers that are characteristic of cuboid growth. It is possible the diamond was only bound by {1 1 1} faces but had a malformed habit, making it more tetrahedral in appearance that was mistaken for cubo-octahedral (Sunagawa, 2010). While the sample did show evidence of moderate nitrogen partitioning between the two sectors, 23–29 ppm in the {1 0 0}, 42–57 ppm in the {1 1 1}, it does not exhibit the large overall nitrogen concentrations and differences between sectors seen in all other mixed-habit diamonds (see above). Combining these two observations leads us to conclude that this sample did not contain any true cuboid growth, and as such the study’s conclusion that no fractionation takes place in natural mixed-habit diamonds is unsubstantiated. As a result, there is clearly a lack of detailed nitrogen-isotope data from mixed-habit diamonds available in the literature to discern whether the preferential partitioning of nitrogen in {1 1 1} growth sectors results in significant isotopic fractionation in the mantle. Thus, this process may or may not result in large isotopic excursions through solely intra-mantle processes.
Here we present N-isotope and N-concentration data, as well as C-isotope data, from three mixed-habit diamonds obtained via SIMS, with improved analytical precision (0.5–0.9‰) and accuracy (<1.5‰) compared to earlier studies (Bulanova et al., 2002, Hauri et al., 2002). Firstly, we investigate whether nitrogen isotopes show any preferential fractionation between growth sectors and compare these findings with those from HPHT synthetic diamonds. Then we use these nitrogen-isotope data to further refine our understanding of how these unusual diamond crystals form, and to better constrain the behavior of nitrogen during diamond formation in the mantle.
Section snippets
Samples
Three mixed-habit diamonds were analyzed in this study (Fig. 1); they were taken from the collection analyzed by Howell et al., 2013a, Howell et al., 2013b. As the samples were obtained from the gem industry, their geographical source is unknown. They are all in the form of doubly polished {1 0 0} plates, ranging in size from 7 to 10 mm (longest axis), all less than 1 mm thick. The previously obtained spectroscopic and carbon isotope data (Howell et al., 2013a) and LA-ICPMS data (Howell et al.,
Results
In total, 134 carbon-isotope and 91 nitrogen-isotope and N-concentration measurements were made on the three samples. All of the individual analyses discussed below are provided in the Supplementary Data Table, with a summary of each sample given in Table 1.
Analyses (n = 46) of both carbon and nitrogen isotopes were obtained from transects of MC08B (transect XS2, n = 20) and MC08C (transect XS1, n = 26), Fig. 1, Fig. 3. In both transects, the analyses were performed at ∼100 μm intervals, with the
Discussion
While the focus of this study is the new nitrogen isotope data from these mixed-habit diamond samples (discussed below), it is important to first make two observations on the reproducibility of the carbon-isotope and nitrogen-concentration data. Firstly, the C-isotope data recorded from MC08 in this study are in complete agreement with the previously obtained data from this sample (Howell et al., 2013a). Also, the ranges of C-isotope data obtained from MC10 (δ13C = −8.37‰ to −8.79‰) and MC13 (δ13C
Conclusions
The new SIMS methodology for δ15N analysis presented in this study has greatly improved the data quality (both accuracy and precision) for this in-situ technique. It is now at the point where it can provide valuable insights into the stable-isotope systematics of individual diamonds. The homogeneous δ13C and δ15N data obtained for three mixed-habit diamonds in this study suggest they grew from a constant homogenous medium in an open (non-fluid limited) system. In the absence of internal
Acknowledgements
Pierre Cartigny, Ben Harte and an anonymous reviewer are thanked for their constructive comments that helped to improve this manuscript, and Marc Norman is thanked for his editorial handling. Tom Chacko is thanked for helpful discussions. RS would like to thank EPSRC and the DTC for provision of a PhD studentship. The CCIM acknowledges operational funding from the Canada Foundation for Innovation, Alberta Innovates, and the University of Alberta. This contribution relates to CCIM project P1301.
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